Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
  • C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/16—Halogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
  • C08K5/57—Organo-tin compounds
  • C08K5/58—Organo-tin compounds containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/18—Homopolymers or copolymers of nitriles
  • C08J2333/20—Homopolymers or copolymers of acrylonitrile

Definitions

• This invention relates to solutions of copolymers of acrylonitrile and vinylidene chloride stabilized with a tin compound against action of heat.
• stabilizers for polyacrylonitrile and copolymers of acrylonitrile containing more than 80% of acrylonitrile. Such stabilizers are intended to protect fibres and films prepared from this material against discoloration under the influence of elevated temperatures. Such discoloration can even occur during the preparation of the fibres and films, for example during the preparation of the spinning solutions, during the spinning process itself and during the subsequent fixing and crimping of the fibres. Unfortunately, the aforementioned stabilizers cannot be used to protect fibres and films prepared from copolymers of acrylonitrile with vinylidene chloride containing 20 to 60% of chlorine, against discoloration under the influence of heat.
• copolymers of acrylonitrile with vinylidene chloride containing at least 20% of chlorine, and copolymers of acrylonitrile containing at least 80% of combined acrylonitrile is embodied in peculiarities characteristic of polymers.
• Each of the two copolymers is clearly soluble in dimethyl formamide. It is not possible, however, to mix solutions of the two copolymers in dimethyl formamide together without the formation of two phases, nor can a mixture of the two polymers be dissolved without the formation of two phases.
• the limit at which the polymers are compatible with one another in dimethyl formamide solution lies at the content of about 28% of combined vinylidene chloride.
• Polymers of vinylidene chloride alone and also those containing a small amount of a copolymerization component become insoluble in any type of solvent during their preparation.
• the different structure of the three types of copolymer which is shown by differences in their solubility, explains why the depolymerization reactions which each of these copolymers undergoes at elevated temperature, are basically different and are inhibited by dilierent types of stabilizers.
• Organo-tin compounds particularly dialkyl tin laurates and similar alkyl tin derivatives, have proved to be highly effective as stabilizers for polymers of vinyl chloride and its copolymers and also for a number of other chlorine-containing synthetics, so that in spite of the fairly complicated processes by which they are manufactured, tin compounds of this type'have been widely used. More simple inorganic and even organic stannous salts have been proposed to protect solutions of polyacrylonitrile and its copolymers containing more than of acrylonitrile, against discoloration under the infiuence of heat.
• stannous chloride is particularly noticeable When it is used in combination with a small quantity, for example 0.001 to 3 parts by weight, based on polymer, of a concentrated acid, such as concentrated hydrochloric acid or, for example, hydrofluoboric acid.
• a concentrated acid such as concentrated hydrochloric acid or, for example, hydrofluoboric acid.
• the much more expensive alkyl tin compounds have a less intense stabilizing effect on these polymers.
• Stannous and stannic chloride are not at all in Water for 1 hour at 70 C. and then heatpectively, at 140 C. The ored is then measured.
• pol stannous sulphate used in very la heat treatment for 4 and 8 hours not contain any other additives.
• the other solutions conare extruded from the solutions, washed in water for one tain the specified quantities (expressed in percentages by hour at C., and then heat-treated for 4 and 8 hours, weight, based on polymer), of the tin compounds listed respectively, at 140 C. The extent to which they are disin the following table. Films are extruded from the solucolored is then measured.
• Example 9 10% by weight solutions of a copolymer of 95 parts by weight of acrylonitrile and 5 parts by weight of methyl acrylate in dimethyl formamide, are prepared.
• Solution 1 which is used as the comparison solution, does not contain any other additives, whilst the following solu- PERCENT Alter 4 hours ageing at After 8 hours ageing at CJnnm 0.).1nm
• Solution Stabilizer 400 450 500 550 600 400 450 500 550 600 1 Noadditives... 75.4 79.6 83.4 87.2 89.8 64.9 73.3 79.5 84.6 88.0 2 0.24% SMBFM. 5.8 15.9 27.3 36.6 42.9 1.5 6.0 15.9 27.6 37.8 2 0.47%Sn(BF4).
• tions each contain the specified quantities (in percent by weight based on polymer), of tin compounds.
• the solutions are aged for 16 hours at 80 C. in thermostats. Films are extruded from the solutions, washed in water for 1 hour at 70C. and heat-treated for 4 and 8 hours, respectively, at 140 C. The extent to which they are discolored is then measured.
• Example 8 It 18 apparent from the measured data that both stanby weight solutions of a copolymer of parts by weight of acrylonitrile and 40 parts by weight of viuylidene chloride in dimethyl formamide are prepared.
• Solution 1 which is used as the comparison solution, does not contain any other additives.
• the following solutions each contain the specified amounts (in percentages by weight, based on polymer), of tin compounds.
• the solutions are aged for 16 hours at 80 C. in thermostats. Films are extruded from the solutions, washed in water for 1 hour at C., and heat-treated for 4 and 8 hours, respectively, at 140 C. The extent to which they are discolored is then measured.
• Example 10 10% by weight solutions of a vinyl chloride suspension polymer (Vestoiit S 70) in tetrahydrofuran, are prepared.
• Solution 1 which is used as the comparison solution, does not contain any other additives, whilst the other solutions each contain the specified quantities (in percent by weight,
• a composition comprising a copolymer of acrylonitrile and vinylidene chloride having a chlorine content of 20 to 60% having therein 0.001 to by weight referred to the copolymer of a tin salt selected from the group consisting of stannous chloride, stannic chloride, stannous bromide, stannic fluoride, stannous borofluoride and stannous tert.-butyl salicylate and 0.001 to 3 parts by weight referred to the copolymer of a strong mineral acid selected from the group consisting of concentrated hydrochloric acid, sulfuric acid and hydrofiuoboric acid.
• a tin salt selected from the group consisting of stannous chloride, stannic chloride, stannous bromide, stannic fluoride, stannous borofluoride and stannous tert.-butyl salicylate and 0.001 to 3 parts by weight referred to the copolymer of a strong mineral acid selected from the group consist
• a composition comprising a solution of a copolymer of acrylonitrile and vinylidene chloride having a chlorine content of to 60% in a polar organic solvent selected from the group consisting of dimethylformamide and dimethylacetarnide; containing 0.001 to 5% by weight referred to the copolymer of a tin salt selected from the group consisting of stannous chloride, stannic chloride, stannous bromide, stannic fluoride, stannous borofluoride and stannous tert.-butyl salicylate and 0.001 to 3 parts by weight referred to the copolymer of a strong mineral acid selected from the group consisting of concentrated hydrochloric acid, sulfuric acid and hydrofiuoboric acid, said copolymer being present in said solution in an amount of from 5 to 3.
• a composition according to claim 2 wherein said composition contains 0.1 to 1.5% by weight referred to said copolymer of said tin salt.
• a compositionaccording to mineral acid is hydrochloric acid.
• a composition according to tin salt is stannous chloride.
• a composition according to tin salt is stannic chloride.
• a composition according to tin salt is stannous borofluoride.
• tin salt is stannous tert-butyl salicylate.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (3)

• 0
  • GB GB1054147D patent/GB1054147A/en active Active
• 1964
  • 1964-08-27 DE DEF43834A patent/DE1224484B/de active Pending
  • 1964-08-27 DE DEF43836A patent/DE1224485B/de active Pending
• 1965
  • 1965-08-06 US US477921A patent/US3376254A/en not_active Expired - Lifetime
  • 1965-08-25 BE BE668753A patent/BE668753A/xx unknown
  • 1965-08-25 NL NL6511113A patent/NL6511113A/xx unknown

Patent Citations (3)

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